JPS58215647A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material high in sensitivity and forming an image high in contrast and high in max. density, by using its emulsion layers consisting of upper and lower layers contg. specified grain size silver halide emulsion, and said lower layer contg. internally fogged silver halide emulsion. CONSTITUTION:The silver halide emulsion layers 2 consisting of upper and lower layers, and a protective layer 3 are successively laminated on a support 1 to obtain the present silver halide photosensitive material, and the upper layer contains a photosensitive silver halide emulsion and the lower layer contains the photosensitive silver halide emulsion, and an internally fogged silver halide emulsion. The silver halide grain size of the internally fogged silver halide is smaller tha those of the photosensitive grains of both layers. As the method of fogging for preparing a silver halide emulsion having fogged nuclei in the inside, the following methods are usable: Illumination with light or X-rays, and chemical formation using reducing agent, golden compd. S-contg. compd., etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel halogenated phosphor material, and more particularly, to a halogenated phosphor material that provides an image with high sensitivity, high contrast, and high M density. It relates to true photosensitive materials.

Regarding a photographic painting consisting of a trowel, the optical density of the image and the image 1
! The ratio of the amount of light per canopy in the navigation plane that makes up the image is generally called the covering power, and is used as a measure of the optical efficiency of the fly that makes up the image. In general, the fμ force applied to the halogenated λ transparent layer increases as the size of the halogenated medium grains becomes smaller, and decreases as the grain size increases. On the other hand, the sensitivity of the silver halide emulsion layer generally increases as the size of the halogenated button grains increases, so halogenated button emulsions with large grain sizes are not used in high-sensitivity photosensitive materials. do. Therefore, in order to obtain high-sensitivity photographic photoresistance, (1) a large degree of sensitivity is required in order to obtain clear image quality. If one color is added, in order to obtain both high sensitivity and the required image density, it is necessary to contain more of the button per area on the photosensitive material. This was the reality of conventional high-sensitivity photographic materials.

In the present invention, the grain size of silver halide is expressed by the grain diameter in the case of spherical or modern grains, and (I
In the case of particles of shape b (for example, cubes, flat scales), the diameter of a sphere with the same volume is used as the table.

As an attempt to improve the crushing force while maintaining high sensitivity, a technique of adding a polymer in the middle of the membrane to the halogenated hook hole side of the high-sensitivity bright phase particles was published in British Patent No. 1゜01, TL, 0 Layer 7. , No. 1,03F, 1771, U.S. Patent No. 3,
0II3, No. 427, No. J, No. 91g, tit No. 0II3, No. 427, No. 91g, tit. All of these have a slight effect on increasing the ability to be trained, but they are not sufficient.
Also, the strength of the coating film is weak (d), and θ7 is not good.

In particular, with automatic leveling that is commonly used today, if a coating with a weak strength such as TI is used, it will dissolve in a 51-I solution or a constant P% solution for a portion of gelatin in the film. Dead weight 11
This causes an inconvenience in that it adheres to the conveyance roller of the image and is transferred to the camera rod 1, causing contamination of the photographic image.

On the other hand, U.S. Patent No. 2. Tata T, No. 31.2 and *3.
I7r, , 2g-Is. outside of each specification, Table 1 shows latent image type halogen intermediate coarse particles and halogenated hooks with fog nuclei inside. It has been described that halogenated substances can be used as photosensitive materials to obtain photographic images with high contrast and high sensitivity.

According to this method, the mourning face S image type halogenated coarse particles are first developed, and the particles generated by this dust together attack the halogenated button fine particles having Capri cough inside the vicinity and cause the development. It is considered a thing.

However, since this method uses highly sensitive phase particles and internally overlapped microtons (quadruple particles), the shape of the developing button tends to become large mottles, and the graininess is poor and the color tone of the obtained two peaks becomes brownish. There is also the problem that when i7 is used in an automatic processor or the like, it causes cavities to form on the photographic material if it is passed directly from the developing bath to the fixing bath without passing through the stop bath.

Accordingly, an object of the present invention is to provide a halogen (t) photosensitive material that provides images with high sensitivity, high contrast, and high maximum pI.

A primary object of the present invention is to provide a halogen-filled Φ1x3 true light-sensitive material with improved graininess and a dark black tone.

The purpose of the present invention is to eliminate dirt without using a stop bath.
+Providing a halogen-based photosensitive material that does not easily cause scratches.

In order to achieve the above objectives, the inventors of the present invention have conducted intensive research and have finally discovered what can be achieved using the following image. That is, in a 111th order Lr halogenated t,lAXP photosensitive material in which a halogenated hookhole side layer and an upper layer are formed on a support, the halogenated hookhole side layer has at least a -F layer and a lower layer. It consists of two layers, the F99 layer contains an F-light halogenated p-hole side, and the F layer contains an R-light halogenated complex and a halogenated emulsion with a rough interior. , the photosensitive i halogenation ω of the upper layer
No. 11 can be achieved by making the grain size of the halogenated button on the side of the photosensitive halide complex pore of the lower layer larger than the grain size of the halogen grain which is internally rugged.

Upper layer scenery r1. used in the present invention. Halogenated button emulsion) and photosensitive lower layer? 4=Halogen tidy 1 It may be the same thing as the halogen powder, or it may be a different one. Regarding the sensitivity, it is preferable that the sensitivity of the photosensitive halogenated emulsion in the lower layer is equal to or lower than the sensitivity of the light-sensitive halogenated emulsion in the upper layer. More particularly, it is preferable that the sensitivity ratio of the photosensitive halodane layers of the upper layer and the lower layer is i:i, s to 100:/.

More specifically, /:/, j to 10:/ are preferred.

In the present invention, "#photosensitive" means -photosensitive halogenation value of the upper layer,'! This means that the sensitivity IW of the PI agent or the lower layer (the sensitivity IW of the halogenated emulsion side is higher than the sensitivity of the internally covered halogenated hook emulsion.More specifically, This means that the sensitivity is 10 times or more, more preferably 100 times higher than that of P deer on the hole side.

Here p, degree and (1, same as the sensitivity shown in F below, it is a constant sparrow.

Photosensitive halogen mori hole side rr is t and the surface latent image type milk f
Conventional halogen emulsions such as i11 are used.

Here, the halogen mori hole side of the surface fj (fang bar 1) melts, /
~//When imaged by the method of surface f1 flight (A) and the method of internal destruction (13) shown in H1 after 100 seconds of light, the sensitivity obtained in surface image (A) is an emulsion in which the sensitivity of the former is higher than that obtained with the internal compound (B), preferably an emulsion in which the sensitivity of the former is j 4g, 9J higher than that of the former. Sensitivity here is determined by the following method.

S:' □-- Eh 8 is sensitive, Eh is maximum fmrF, (IJrn;
+x) and the minimum sea level (1,)min) 1+'kmaro-(J,)max +Dmin
) is the amount of light required to obtain the tuna.

[Surface] [1st body (A)] Developed for 70 minutes at 200C and Thf in the sputum of the lower H "prescription".

N-methyl-p aminophenol (Hemi value 1 k) J,! 9 Ascorbic acid 109 Sodium metaborate, Tetrahydric acid 1-339 Potassium bromide
/2 Add water
/l [Internal phenomenon (B)] Treated in an egg white solution containing blush i3p/z and phenosafnin 0.072t9/l at about 100c for 70 minutes, then washed with a water bottle for IO minutes and then treated with a dust bond solution prescribed by Shimoeki. Incubate at 200C for 1 minute.

N-methyl-p-aminephenol (hemivalent acid salt) -2,tq
Ascorbine combination ioy meta bolic acid sodium hydroxide, Yosuiba 3? potassium bromide
/2chioibi fNJ/
Soda 32 Add water
/ surface #1 quadrangular halogen f
It is preferable to use a material containing iodized casting, and specifically, 6-1 silver iodobromide and iodobromide button can be used. Here, Iokaga's blonde hair is O0/~30 moles, especially 0. It is preferable that the imprint 1 is jt~70 mol %, and the 0° average grain size is preferably larger than that of a halogenated silicon emulsion having fog nuclei inside, especially θ, , g B
tnn is preferably 2. The particle size distribution may be narrow or wide. Halogenated C in emulsion
I-particles are regular particles such as cubes and octahedrons.
ar) may have a crystal shape, or may have an irregular crystal shape such as a spherical shape or a plate shape.1. The first meeting of the crystal form 3? The talent of glaze crystal form, even if it has
The resultant force to the soup of the eggplant may be I+Q-fu.

The photocopy milk ^11 used in the present invention is P, (monthly afkid
Written by Jhimie et Physique Ph
otographique (Paul I\Iont
Published by e1 company, /riothui f:, ), U, F.

Written by IJL Hyakufin Photographic Em
ulsion('hemistry('ll'he
Published by l'ocal Press, /Riotsu6i) Moon, V
, L., Zelikman et a1%Maki
ng and C, nating Photogr
aphicEmulsion (1'be l'□
R1' published by cal k'ress, /ri 6J), etc.
I(1') can be prepared using the same method.

That is, any of the V1 method, neutral method, ammonia method, etc. may be used, and the 11 methods for reacting the soluble halogen base with the soluble halogen base include the 1011 mixing method, the simultaneous mixing method, and the like. You can do anything like bag matching in January.

Method of forming a ladle under hook ion JNl (
A so-called 1ψ mixed method) can also be used.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which halogenated particles are produced can be kept constant, that is, the so-called Chondrald-Duffle jet method can also be used.

If you use this method, the crystal form will be 1j14. It is possible to change the halogenated layer emulsion which is regular in size and has a nearly uniform size.

Formed separately. Halogen value nipples (I) having a halogen value of 2 or more may be used in combination.

The formation of halogenated particles is in the 16th verse of physical ripening. It is also possible to coexist a group or a complex tλt.

Features of the present invention')'f: As a halogenated needle with a fogged nucleus inside used for the material, 9 sl @ 227 m
2 What is the test piece coated on a transparent support? J
-With D-/9 (Eastman Kodak Co., Ltd.) for 1 λ min. Then, the same test 1. Without exposing the dye strip, 1)-/ was mixed with a liquid solution containing θ, jF?/l-, and 3!'C,
, 2 minutes fl, defecation @/, Transmission turnip L-1 of O or more
An emulsion giving f (excluding the f4 degree of the support itself) should be used.

A halogenated silicon emulsion having fog cores inside can be prepared by known techniques. The fogging methods include irradiating light or X-rays, chemically creating capri cores using reducing agents, gold compounds, or high-value yellow compounds, and emulsion fabrication with low pAg and high pt There is a method such as fogging only the inside.
77. There is a hand-finished bowl in which the surface of the bowl is covered with nickel silver using blush salt, but IJ'? Scary is Masu Low +111 A
, +2 , How to prepare a core I agent with a capri core by a chemical fogging method, and then add this core! This is a method of covering the area around the yl cut (r shell emulsion 1).This core shell!
! Ll! The law is known and implemented, for example in the United States1.
? 'ifl'il?' 3. 20 Otsu, please refer to item 11 of Specification No. 373.

Halogen value emulsion 1, which has internal fogging, has a negative side effect of 1.
It has an average particle size smaller than that of the square-shaped halogenated button milking, and preferably has an average particle size of /, Qltm or less, and is preferably 0.1μ? It is more preferable to have a uniform grain size of 31 nm or less of 4-1, and particularly preferable to have a particle size of 0.15 μm or less, which can give good results.

In addition, as the internally covered non-loginated button emulsion, any one of Su, Kakaku, Hōguka CI+, Bromide Hoko, Junbrobromide, Tsuron 111: Mei, etc. may be used.

The mixing ratio of the halogenated emulsion used in the lower layer of the photographic light-sensitive material of the present invention and the internal halogenated needle hole side is 1. Although it can be changed depending on the contrast of the Kantake 1 and 4 agents used, θ-L or 100;/7)-L/:100, especially 10:/
From /:10 is preferred.

The total coating ratio of the upper layer and the lower layer of the halogenated tablet hole side layer varies depending on the emulsion used, the application, etc., but is preferably /:j) to 10:/, and preferably /:3 to t. / is. Also, considering the ratio of declaration to light τ fraud rate after the current ward, /:10 to 10:/ is favorable, /
; 5 to 5: l is ↓ liquid, ``secondary'' −1 It's okay.

The halogenated emulsion layer may have an upper layer and an overlapping layer containing a halogenated emulsion.

The upper layer and the lower layer were placed in a 1/1 halogenated photosensitive ladle. ...Vr is good if there are 7 layers of rogenized hook feather cutting layer, but it is not necessary to have 2 or more layers (V/ll is 31 units).

The rogogenation value of the present invention! 4. The false layer of the photosensitive material is a layer made of colloid, and the hydrophilic colloid used is as described above.

The Howa I layer that was cut can be a single layer or multiple layers.

In addition to this, the non-rogenated φP photosensitive material of the present invention may be provided with an anti-warf layer, an intermediate layer, a filter layer, etc., depending on the requirements.

The single emulsion used in the present invention is usually removed by soluble pouring after precipitation or physical ripening, but Knoop J. A water washing method may be used, and inorganic salts consisting of monovalent anions, such as
, Anion Dokai RF + i activity? J: ? ft4% using anionic polymers (e.g. polystyrene sulfonate) or gelatin derivatives (e.g. fatty acid acylated gelatin, aromatic annated gelatin, aromatic carbamoyl gelatin, etc.)7. to (70:
V Yurezoyon) wo If I temo good.

Approximately 1tlJ of soluble liquid removal may be omitted.

Photosensitivity: A so-called primitive emulsion without chemical sensitization can be used, but chemical sensitization is usually used. For chemical sensitization, pre-AIF, u I; + f k i d
e s or the book by Zelikman et al.
, I'rieser 1iAshiie ()rundL
+gen der I'photographbisc
henf'rozesse mlt 5il))erh
alp)! eniden(AkademiScl+e
VerlagsgeSellshaft.

The method described in 6g) can be used.

In other words, a compound l+ that contains a yellow pigment that reacts with a button ion.
Kayo sensitization method using activated gelatin, reduction sensitization method using reducing substance 1, gold and other prizes can be used in combination with compound 1, jb sensitization method, etc. , As the agent, thioIA acid salts, thiourea, thiazoles, rhodanines, and their (IL+ compounds) can be used. Gu 94/Gu No. 1, :z, 1iio, tyry
No. 1.2. ．． 271. Tag No. 7, ), 7.2J, Jg+
r number, 3. Otsu-IJ, No. 755, u, 03.2. !
P, ZIr No., '1,0/, described in No. 7.7410 -4 color. As reduction sensitizers, stannous salts, amines,
Hydrazine derivatives, 1-luno, amidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof can be found in the US publication No./LF7.130 1. y,,v
Iri, No. 9741-! , j/ and tri♂ No. 1, 2, 7
13, tOri issue,! , Ri♂3.610, Ko, Otsu? G, t37 No. 1, de, ri 30, l? A7, 4t, 0
! F11, 1131 has a lip [4 years old].

For noble metal sensitization, in addition to gold@salt, complex salts of metals in Group II of the Periodic Table, such as platinum, Iridium 1%, and Paratium 1%, can be used.
3tata, Or3, same, 4t<tt, oto,
British Patent No. 6/♂, No. 067 is ¥it f&.

Various hydrophilic colloids can be used as binders in the photographic material of the present invention. Examples of colloids used for this purpose include gelatin, colloidal aluminum, polysaccharide, cellulose conductor, and synthetic resin. For example, hydrophilic colloids commonly used in the photographic field, such as polyvinyl compounds containing polyhinyl alcohol conductors and acrylamide polymers, can be used. Along with the hydrophilic colloids, hydrophobic colloids such as dispersed polymerized hinyl compounds, especially those which increase the dimensional stability of the photographic material, can be included.

Suitable examples of this compound include water-insoluble polymers made from vinyl thread monomers such as alkyl acrylates or alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates.

In the '4 True Breasts 11 of Joropi, the product of Sensitivity Lt 1 is about 1-1, and a compound of loincloth is added to prevent the occurrence of sensitization and cuff IJ (7) during preservation or processing. Be able to do it.

Those compounds are goo-hydroxy-t-methyl-/.

33a 7-detrazaintene, 3″″ methyl-benzothiazole, /-phenyl-j-mercapdobutrazole, and many ″0 ring compounds 1, hydrated complex compounds)
A very large number of compounds such as , mercapto compounds, metal salts etc. are predicted.9. I know l+.

An example of a compound that can be used is k, M e c s
Author: ``The 'l'heory of the, P
photographicL no rocess” (3rd edition,
The original documents listed are p., U.S. Patent No. 1, 7jfl.

No. 576, same No. 1, /10. /7g issue, same issue, 2゜i3
/, No. 03Ir, same f, 2. /73. A2 # No. 2
, 6ri 7.0qO issue, same issue! , 30g, ri/, No. 2, No. 2.3.2, No. 23, No. 2,374tl19
No. g, No. i, tttti-, tor ~ No. J', No. 1
4. z, tga, z<zj issue, same number 2.6! P11,7
/No. 6, No. 6, No. 6, 7.0 Tata No., No. 7, 7or,
i6.2, M, 2.721f Mamoru t3~! No., same dJ
, 2.4'7A, jJA No., 2,1217,00
/ No. J, 1t13, No. 447, No. 2.
Su♂t, Gu No. 37, Same No. 3', 0!12. J gugu issue, same number 3. /37,377, No. 31.2, O9 and No. 3, No. J, 2.26, 23/, No. 3. ．． 2.3
A, Aj, No. 2, No. 3. ．． 23/, Ari No. 7, Ari No. 3
Ko! ;, 2,7 Tata No. 39.2♂7. /Js issue, 3.3.21! l, 6za No. 7, same No. J, 4', 2
θ.

+g, r issue, same number 3. A, No. 22,339, UK Telephone 193. II), No. 1, No. 1103.71'Y,
Same 1st. /73, No. 60, No. 1. ．． 200. /1 and the number are 0 self clause 7.

In the light-sensitive material of the present invention, the emulsion layer and other hydrophilic colloid layers have an additional hardness of 100%.
,! It can be hardened with an agent. Tokukaisho! These hardeners! 3-7AO,! No. j, same j3-71.0.2
Same as the issue! Examples include hynylsulfonyl compounds such as those described in No. 3-774/2; oxypolysaccharides such as dioxane derivatives; and dioxane derivatives having halogen as active radical;

Other additives, particularly those useful in photographic emulsions, such as d'AI additives, sensitizers, light-absorbing dyes, r3j additives, etc., can be added to the cutting tool halogenated complex emulsion layer.

Furthermore, in the present invention, iodine is added to the halogenated button hole side.
A desired image can be obtained by using a compound that releases ions (such as potassium iodide), and by using a developer containing iodine ions.

In the photosensitive material of the present invention, a filter dye may be added to the hydrophilic colloid 1-, or a water-soluble dye may be added for prevention of irradiation, prevention of halation, and other purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, melonanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the light-sensitive material of the present invention, when dyes, extraneous radiation absorbers, etc. are added to the hydrophilic colloid, they may be added to a cationic polymer or the like to be mordanted. For example, British patent 6, Gutu J, US patent -, lr7! ,3
/No.6, same J, l'3ri.

Gu O/issue, same! , err, ist issue, (iJ3.
'lIf, 1ItV issue, same 3. /III, No. 309, 3° + L4Zj, No. 23/, West German patent fi ((
JLS)/.

Polymers described in JP-A No. 41, 36.2, JP-A-1174-1174, JP-A No. 30-7/JJj, etc. can be used.

The photosensitive material of the present invention may contain a surfactant for each purpose. Depending on the purpose, nonionic, ionic, or amphoteric surfactants can be used; examples include polyoxyalkylenes, conductors, amphoteric amino acids (sulfobetaines are also included), etc. L. Such surfactants are available from Japan Percent Co., Ltd., No. 100°1.3/US, ff., 2. ,
! 7/, A, No. 22, American ff-2,,2
7/, t, :Z3+”;, US Patent λ, z7i.

No. 7.27, U.S. Pat. No. 2.7g7. No. t04, U.S. General Fraud Co., g/&,'ri No. 20, U.S. Patent Co., 73
the law of nature.

It is described in Niri No. 7 and Belgium %πfA3.2, No. 16.

The 1'' C4 emulsion of the photosensitizer of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. Dyes such as merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopholarianine dyes, styryl dyes, hemicyanine dyes, oxonol hornine, and hemioxonol dyes can be used.

The Ichikawa sensitizing dye conveniently used in the present invention is, for example, US special #'f3+! 2.2.03, issue, 3,6/ri,/
7/3, 7/3, 1.21, 3. AI! .

6μ3, same 3. AI! r, l, No. 3.2, same, 3,
477,. No. 293, No. 3, No. 6.21.96μ, No. 3
゜703.377, 3, J4A, lI&'0
No. 3, lt7,9tO+;, 3. A79, 11.
No. 21, 3. t7.2, 127th, 3.7t, 0
．． No. 2, No. 43, Jet, Roo, No. 3. AI
! , A/3, same 3, Al6.631, 11" 3,
1. jet.

No. 633, No. 3,70, No. 1gO, No. 3,63, 3
Geta issue, 3,677.76! No. 3゜'770,
II Hiroshi No. 9, same J + 770.4”I (1)
吋, same 3.767, θノ! No. 3, 7&j, 0
/G issue, 3, 7/3, 1λg issue, 3. ! ls7. gujg issue, line 1-13, 6 no 1. +ri g, four,,t,
2A, No. 43.2, same, No. 303.776, JP-A No. 1
27Aj, No. 2j, Belgian Patent No. t/, No. 107, etc.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in Tokuhata's negative working/% rogenated complex emulsion. In particular, it is advantageous to use the dye concentration at a level that does not actually reduce the inherent sensitivity of the halogenated complex emulsion. Halogenated @ approx./mol of sensitizing dye.

oxio ~ about s>io mole, especially /10
Approximately 4t% of sensitizing dye per mole of silver germide/θ ~, 2
It is preferred to use a vN of >10 mol.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a soft support such as a plastic film, paper, or cloth, which is commonly used in photographic light-sensitive materials, or a rigid support such as crow, pottery, or other materials. Put A1 cloth on one or both sides. The most commonly used flexible supports are cellulose nitrate,
Cellulose acetate, cellulose acetate, polystyrene,
Filno 5 consisting of semi-synthetic or synthetic polymers made of polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layer or α-olefin polymer (1
It is a laminated paper, coated with polyethylene, polypropylene, ethylene/Latin copolymer, etc. The support may be colored with a dye or pigment. Black for the purpose of blocking light. Even if it's a banana, it's hard.

The surface of these supports is generally treated with F'S to improve contact with photographic emulsion layers and the like. The surface of the support is treated with corona discharge, ultraviolet irradiation,
You may perform Odomari processing temple.

In the Yoshin photosensitive material of the present invention, the photographic milk layer 11 and other hydrophilic colloid layers can be coated on the support or other surface by a known coating method. For the inner fabric, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. US patent! ,6za/,-
Fugu issue, same! , 76/, 7ri No. 7, same! ,3J,A,!
2r No. i] "[The method described is an advantageous method.

In the protective layer or protective layer of the present invention, a matting agent and/or a matting agent are preferably included in the protective layer.
Or you can add a smoothing agent etc. An example of a matting agent is a material with a small particle size (preferably one with a diameter of 0.3~Jμ, or one with a diameter of at least twice the thickness of the sleeping layer, and one with a thickness of V times more than 100%). Preferably used are water-retaining polymers such as polymethyl methacrylate, organic compounds, and inorganic compounds such as strontuno, valium, and the like. Smoothing agents help prevent gradual failures similar to matting agents 11! ! It is effective in improving the 1iA drop in camera precision during filming or projection of movies, and specific examples include liquid paraffin, esters of commercial fatty acids, etc. Waxes such as polyfluorinated hydrocarbons or derivatives thereof, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyargylarylpolysiloxanes, or noricones such as alkylene oxide addition derivatives thereof are preferably used.

The present invention can also be used for photosensitive materials that require high sensitivity or high contrast. For example, X-ray photographic materials, lithographic photographic H
It is used for L materials, color negative photosensitive materials, color paper photosensitive materials, etc.

In addition, the undeveloped halogenated non-halogenated material is dissolved in +W L, and is applied to the image receiving layer 1 or 1 in proximity to the halogen value emulsion layer, thereby creating a positive light-sensitive H material, a color diffusion transfer ring source. +71 fee can also be used monthly.

The photographic λ treatment 0C of the photosensitive material of the present invention is 1.9jj
Jisclosure) / 7 A No.
2J'~30-White (RJJ-/76≠3), any of the known methods and known treatment liquids can be used. This odor processing can be done depending on the purpose.
, or (photographic processing (color shutter, processing) that forms industrial pigment Ii#.Process il+4! Humidity is old oil 1r0c or L:)! Although chosen between 0°,
/do0(j-lower temperature -f /C may be a temperature exceeding !O0C.

Example", Kuroto] 1MM used for photographic processing
' may include known developing agents.

Development Wangwei and his colleagues also use dihydrogyzobenzenes (for example, hyde [goquinonone, 3-hishisoridone (IL t9..rJ, /-)], di-3-pyrazolidone, aminephenol wholesaler (even kA' N- Methyl-p-aminone enol), etc. can be used in the form of a cliff).
For this purpose, it is also possible to treat the halogenated complex solution with a koji malt solution containing imitazole as the halogenated complex solution. Also, Tokusuna Akira jA-
/31. ．． It can be processed with a developer containing halogenated melt cutting described in No. 2A7 and final cutting of indanol or triazole. In addition, there are some known preservatives, alkaline shavings, anti-cuffs, etc. for peace of mind. Zhou Gang, usage ov +l!: agent, interface Y old agent, γiM fly cutting, hard water conversion agent, 1st version Al
1, a viscosity-improving agent, etc. may be included.

The hA emulsion of the present invention has a so-called 1-lith type kMA'.
4 treatments can be used for the bottle. 1 Squirrel type "Gen 1 Hanshoban" is the ff of Hayashi's Il~, 5 "True 11 shi reyu, or) - the instrument-like ↓ in the voice of the notone image C) Gen, usually Dihydroxybenzenga is the current Kaishu system and 17,
Low sub-IL acid ions - Under the crest, it is said to be the function of the fJl image that makes the process contagious. /Re 1966)/A3~it, the description is on page R).

As a special form of Dankashohata, a method is used in which the light-sensitive material is processed in an aqueous alkaline solution to facilitate development. Good too. Among the medicines, the hydrophobic one is Lisanna Day Disclosure / No. 1 (T also IJ- / Ari No. 21) US Patent No.!
, 73ri, ruri0inch, UK 1 Clock No. 3/3. ．． 2! No. 3 or west! I11 Special leakage plan 1st. They can be incorporated into the emulsion layer by various methods such as those described in J.Care, No. 763.

This type of development treatment is carried out by Kanhana Anhinkasho J! (May be combined with 1.

As the constant titration liquid, one having a commonly used composition can be used. As a fixing agent, in addition to thiosulfuric acid and thiocyanate, a myelinated α compound, which is known to have an effect as a fixing agent, can be used.

The Teijima liquid may also contain Mizunuma's Aluminum Uno Tan as a hard metal cutter.

SA Example 1 By the ammonia method of the licensed ammonia process on the halogenated button hole side, iron nitrate, Caritas bromide, and Caritas iodide were combed, with an average particle size of /, 3 μ, on the bromide hole side, ( , 2 mol %) was prepared and subjected to gold-sulfur sensitization method, followed by gold-hydroxy-
By adding a suitable amount of 2-methyl-/3,3a,7-tetrazainthene, a photosensitive θ, odor emulsion A was obtained. Using the same ammonia method for dogs, the average particle size was different from that of emulsion A.
A complex emulsion (/, 3 mol%) of /μ was prepared and chemically sensitized by the gold/sulfur sensitization method. 7-Putrazainde 7 Father's power 11 In addition, photosensitive method frog emulsion B
Chew.

(1) Mix 2% gelatin water with nitric acid bath solution, potassium bromide, and blackened sodium at 7:3 while stirring at 0C.
Water and water mixed in a molar ratio were simultaneously added over 12 minutes. Raise the Uzugan to 730C and hydroxylate it)
Riuno? By adding a suitable amount of acid to the mixture and aging for 75 minutes, a fog core was created. After returning the temperature to the original temperature by adding acetic acid and caritas bromide to the original temperature, add ss LcK'5 acetic acid and caritas bromide to the original temperature, then add sss LcK'5 acetic acid and caritas bromide to the original temperature. Mix at a molar ratio of 7:3 and add 1. ! Simultaneously joined for 3 minutes, Tonglu Shen#
By re-dividing into a gelatinous liquid, an internally brominated button emulsion C with an average particle size of 0.0 μm was obtained.

Sample 1: Attractive force of 11 [, 21?] on both sides. On both sides of the polyester base, there is an emulsion layer consisting of a mixture of fnlnl light 1, 1) C, and a storage layer of gelatin aqueous liquid. ) IV1 coat was applied. 771 at this time. (The coating g of the emulsion screen is emulsion A in the layer i/, θW / rzI2,
Emulsion C or i.

0? /m2, emulsion A in the upper emulsion layer was lost at t, oy7m2.

Sample 2 Sample 1 and H bass 111 song, front aL feeling)Y:,
Emulsion layer mixed with brominated button milk ^110 on the inside of the sword, hole side A, Chinese and German emulsion j-, gelatin water 1
The first coat of 441 temporary protective layer was applied. At this time, the coating on both sides of the emulsion Qlt, n; L,
Pore side agent B in the emulsion layer is /, 0? /m, milking C/,
097m.

Emulsion A in the upper layer of the emulsion was 4.0 f/m.

Comparison].

On both sides of the same base as Sample 1, an emulsion layer was prepared by mixing the photosensitive iodobromide button hole side A with the internally fogged salt-permeable hole side C;
Seven Latin water bath liquids were added to the sieve solution. The body cloth plane stones on both sides of each emulsion are nipple lj A is 7,
0 W/”z emulsion layer is /, 09/m2]
It was.

Comparison 2 On both sides of the same base as Sample 1, there was an emulsion layer of the internally fogged button hole side C, emulsion 1- of the photosensitive iodine method alone, and a layer of 1xil + layer of gelatin aqueous solution. 11 "] Next, the wall cloth button toe on both sides of each emulsion is 1llc/, 097m in the lower emulsion layer, and the nipple 1 in the upper emulsion layer.
1A was 7.097m.

After the sample was created bald and wedged with light, the following composition was found: dust 1 house liquid no! OuC: treated for q minutes, then dried under pressure, water fk, ft.

Dust image solution A /-phenyl-3-hycineritone 0.3? Hydroquinone, 20, Qf, Zf
L/Diaminetetraacetic acid disodium, Ci, 09 (
lift acid kaliuno, bo,
OP Hiroshi Hiroshi, 0?
Potassium charcoal, zo, oy sodium bromide, s, oy diethylene glycol 30.0? add water
/l.

Set pH to 70.0 with Na () 11.

The results of sensitometry of the monk obtained are shown in Table 9.

From the results in Table 1, it can be seen that samples with the layer structure of the present invention like Samples 1 and 2 /ζ are similar to the blend type of Comparison 1.
The effect described in Tokuko Shogu/-, 20A♂/ is not known. In contrast to Comparison 1, Comparison 2, in which two types of emulsions were coated as separate, different layers, was significantly inferior in JJ integrity.

Next, Kf-EL, sample 12, can be reported.
and for comparison 1 - K to compare C1 grain v3 properties
m/i? After 7 hits using paper (Shinshi Niruno/Shamo High Screen Standart), the above process was performed to remove H+, M, 8...11. The results are shown in Figure 2.

In the figure, for comparison l, L1 trial Y)1 work 2 of 1(,M
It can be seen that the candy of S has a wide optical density range and a decrease in strength, and compared to Comparison 1, the granular structure of Sample 1 and 2 is outstandingly superior.

The above results show that when using the technique described in Japanese Patent Publication No. Shogu. Which indicates that.

Example 2 Preparation of internal milk shavings (2) ′,! 4 A method similar to the method for preparing the inner grain emulsion described in Example 1 was used to obtain an emulsion with an average grain size of 01-2 μm different from that of Emulsion C.
1 no 1 part 71) I served the four-brominated button emulsion.

Trial No. 13 Wikiage 11 internal sword/furihatobrominated button hole side C instead of PC Jero [) internal η/burihatobrominated buttonhole side 1 non! -t
Samples shown in Figure 1 were prepared. At this time, each emulsion's double-opened cloth carrier is the milk 71j A in the lower layer of the emulsion.
G/, O? /m, milk ql D is /, 0517m, milk AIl A in the upper layer of the emulsion is ls, 0? /m Detsu fc.

Comparison 3 Same test as t1 ratio axis 1 using Uefuda internal sword, fuv1 crystal fuka [with] P hole side IJ instead of internal kafuri chloride bromide button hole AlI C of comparison 1) "Kaoru tone - I was angry. At this time, the milking A on both sides of the milk Ml of each 7L is 7.09. /
m.

Milk shaving was /,09/m2. These sample pieces were then subjected to the same MJflj as in Example 1 and the same results were obtained. The color tone of the obtained color was visually judged and the result was that the color tone of Comparative 3 had a dark J7 tinge, whereas the color tone of Sample 3 was pure black W-4. The above-mentioned nature is that when using 6.9 fine particles, the color of the current color has a darkish tinge, and when using 6.9 fine particles, by creating a layer structure like Honmoto Akira, This shows that the color tone of the image is improved.

夷1Jlfl t71J 3 For samples 1, 2, 3 and 1 and 3, process the multi-sand sample pieces using the -Fd pi process using a Manshi Firno, #RN Mechanical Generator. did.

Processing process current 1$ 330C cojsho fixing 3.29t: , 2 r seconds water washing 32
0C, 2 layers, 4 bales dried 5o0 (: is), cystic stains were observed.

This is a report by Kaoru Omote, which investigated the extent of the dirt and the appearance of Kasumi.

table ! The results in the table show that the samples of the present invention have significantly improved staining compared to the comparative samples71). The second thing is to remove the bamboo II-
71 It has been found that when washing a C table in the direction of λ without using 1115, the porosity and cavities that are present in the river can be improved by creating a layered structure like the one described in this paper. ing.

[Brief explanation of the drawing]

FIG. 1 is a first view of the cup of the photosensitive halogenated button musical instrument of the present invention. Support/, two layers of emulsion 1 mλ and 3
〃・The emulsion layer contains expression 1 latent type milk 7jlJ4. Contains J and internal aphrodisiac type rituals. FIG. 1 is a diagram showing the ratio of R M 8 to the optical angle of Sample 1 of the present invention, Sample 2, and Comparison 1. Patent applicant: Rikishin Fujirino, Stock interest rate @ 1 Figure 2, Draft procedure amendment 2, Name of the invention Silver halide photographic light-sensitive material 3, Relationship with the person making the amendment Case: Patent applicant Location: Minamiashigara City, Kanagawa Prefecture 210 Nakanuma Unosaki Address 4, No. 26-30, 21'' Nishi-Azabu, Minato-ku, Tokyo 106, Subject of amendment Column 5 of “Claims” and “Detailed Description of the Invention” of the specification, Amendment The statement in the "Claims" section of the description of contents is amended as shown in the attached sheet. The statement in the "Detailed Description of the Invention" section of the specification is amended as follows. m Correct ``bad'' in line 7 of page 7 to ``bad. again''. (2) Correct “Question Color ga” in the first line of page 3 to “Question Mo”. (3) From "the upper layer" in line 9 of page j to "largely" in line 72, "the grain size of the internally covered silver halide is the same as that of the photosensitive silver halide in the upper layer and the photosensitive silver halide in the lower layer". smaller than the silver halide grain size of the silver halide emulsion.'' (4) Correct "100 or more" on the 9th line of the page to "700 times or more". (5) "It had a lower layer." in line io of page 13 is corrected to "It had a lower layer." (6) You can use page 1 J in line 1,
Can be used. ” he corrected. (Correct "Silver salt by acid salt" in line j of page 2 of the sword to "silver salt". (8) Correct "sodium hydroxide" in line 13 of page 29 to 1
- with sodium hydroxide”. (9) On page 30, line 73, change “emulsion B” to “emulsion B”
and correct it. Ol Page 31, line 9, rA before "single emulsion layer"
Insert J. OD Delete "significantly" from the first line of page 33. 02 Correct ``Reference sample J'' on line j of the 3rd page to ``similar sample.'' (13) Insert "using developer B5r of F" after "numerous sample pieces" in the third jfJJ line. (J4) @Page 32r, 6th line, correct “imagewise” to “imagewise”. (15) Insert the following theory 8A after the 31st @I/ line. [Developer B Potassium hydroxide C 1. ．． 29. /gghydroacetic acid 10.91. g Potassium sulfite lI-g 0.2og
Sodium bicarbonate 7, JOg boric acid i
, oog diethylene glycol ,! To, ?
Ag engineering (,n/diaminetetraacetic acid HaA7.9 1-methylbenztriazole o,oHj-ditroindazole 0..2 layers 1g hydroquinone 30.0θI/-phenyl-3
- Pyrazolidone /, 50g glutaraldehyde ≠, 93g sodium metabisulfite /λ, by adding Ol water
/l'' Attachment 2, Claims A silver halide emulsion layer and a protective layer are sequentially placed on a support] - Regarding a silver halide photographic light-sensitive material, the silver halide emulsion layer is at least an upper layer. The upper layer contains a light-sensitive silver halide emulsion, the lower layer contains a light-sensitive silver halide emulsion and a covered silver halide emulsion, and the inner layer contains a light-sensitive silver halide emulsion. A silver halide photographic material characterized by:

Claims (1)

[Claims] In a silver halide photographic light-sensitive material in which a halogenated button emulsion layer and a protective layer are arranged on a support in the upper right corner, the halogenated button emulsion layer consists of at least two layers, an upper layer and a lower layer, and the upper layer has a photosensitive layer. Contains a silver halide hole side, and the lower layer contains a photosensitive halogenated emulsion and an internal overlapping halogenated (-nipple 11) 1-1a, an upper layer of photosensitive halogenated silicon, and a lower layer of photosensitive yc- A halogenated silver photographic light-sensitive material characterized in that the size of the halogenated grains of the halogenated hook milking is larger than the grain size of the halogenated grains covered inside.